Mercuri-acetylide compound and method of preparing the same



Patented Sept. 21, 1943 MERCURI-ACETYLIDE COMPOUND AND METHOD OFPREPARING THE SAME Morris H. Daskais, Chicago, Ill., assignor toResearch Corporation, a corporation of New York no Drawing. ApplicationOctober 9,1939,

' Serial No.-298.,635

9 Claims. (01. 260-431) The present invention relates to a new series ofmercuri-acetylide compounds and to methods of producing the same. Itwill be fully understood from the following description, illustrated byspecific examples of compounds of the present invention and theirpreparation.

Various mercuri-acetylide derivatives have been prepared by methodshitherto described; for example, variousbis-alkoxy-alkyl-mercuri-acetylides have been prepared by the method ofNieuwland et al. (J. Am. Chem. Soc., vol. 55 (1933), pp. 2465, 3728) ofwhich bis-p-methoxyethyl-mercuri-acetylide may be regarded as typical.no solubility in water and in weak alkaline aqueous solutions and aresoluble only with difliculty in such organic solvents as methanol,ethanol and acetone. Hence the use of such compounds is restricted,particularly where fungicidal and germicidal effects are desired.

In accordance with the present invention, I have prepared a new seriesof mercuri-acetylide compounds which are characterized by solubility indilute aqueous alkaline solutions or water or both. Y

In carrying .out the process of the present invention, I preferablyemploy a mercuri-acetylide compound of the general formula in which R1represents an alkyl group and R: a hydrocarbon radical of the classconsisting of the aliphatic and alicyclic groups. Such compounds may beprepared by the method of Nieuwland et al., above referred to. I reactupon such a compound with an organic nitrogen compound generally whichhas an amido or imido radical containing a replaceable labile or acidichydrogen atom, thereby replacing the R1O-- or alkoxy group of themercuri-acetylide compound. Organic nitrogen compounds having thecharacteristics above set forth which I have employed in carrying out myreaction include the amides and imides of carboxylic and sulfonic acids,and also various pyrroles and pyrrole derivatives, morpholine and thelike. For example, I have used acetamide, propionamide, urea, benzamide,salicylamide, phthalimide, succinimide, 5,5-diethylbarbituric acid,benzene sulfonamide, amino-benzene sulfonamide, paratoluene sulfonamide,morpholine, carbazole, and pyrrole.

The reaction is preferably conducted in the presence of an organicsolvent in which the reactants are partially or completely soluble. Itis preferred that the solvent selected has a boiling In general, suchcompounds have little or point below the melting point of themercuriacetylide compound used in the reaction and that the reactants becompletely dissolved, although Y acetone, butyl or ethyl acetates orpropionates or the like-may be employed as solvents.

In the resulting compounds, one valence of each mercury atom is bondedto an acetylenic carbon atom and the other to a carbon atom of ahydrocarbon group which is apparently bonded to a nitrogen atom of anorganic nitrogen compoundand preferably to a nitrogen atom of an amideor imido group in the organic nitrogen compound. This structure isindicated by the fact that, when reacted upon with sodium stannite, thecompounds produced yield metallic mercury very slowly as contrasted withcompounds having a mercury nitrogen linkage, which, with the samereagent yield metallic mercury quickly.

The compounds produced in accordance with my invention have the probablegeneral formula The compounds of my invention are-of particular value asgermicides and fungicides, for

example, in the treatment of wood, in cut or uncut form, to preventfungus diseases such as blue stain on lumber, and in the treatment ofseed to disinfect and immunize the same against infection. Thesecompounds are substantially odorless and, for all practical purposes,are noncorrosive to iron, hence lending themselves for use in ironmachinery and the like. An outstanding advantage of the compounds inaccordance with my invention is the fact that they are non-vesicant anddo not irritate or cause blistering of the skin, thereby enabling themto be handled without fear of iniuricusly affecting the operator oruser. I have found that seeds can tolerate large amounts of thecompounds of my invention and the treated seed is stable and undergoessubstantially no deterioration in storage. The following examplesillustrate methods of preparing soluble organic mercury compounds inaccordance with my invention. It is, of course, to be understood that myinvention is not to be construed as limited to the proportions anddetails of the methods therein set forth, since various modificationsthereof will be apparent and are intended to be included within thescope of my invention as defined by the appended claims. In theexamples, the term parts indicates parts by weight. I

Example 1 20 parts of bis-beta-methoxyethyl-mercuriacetylate and 13parts of phthalimide are dissolved in about 300 parts of isopropylalcohol. The solution is refluxed for about two hours, at which time thereaction is completed, and the solvent is removed as by vacuumdistillation. The reaction product, apparently the compoundbisbeta-phthalimido-N-ethyl-mercuri-acetylene, is dried in vacuo. Thecompound is soluble in warm aqueous sodium carbonate and in boilingwater. It sinters at 142 C. and melts completely at 166 C.

In tests conducted by me I have found. that this compound will kill thesap stain fungi, Ceratostbmella pilifera and Graphium rigidum in anutrient agar medium in a concentration less than 1 part per million.This reaction product is. also toxic to the wood rotters, Fomes annosusand Lenzites tr'abea in concentrations of one-half part per million.

The compound bis-beta-phthalimido-N-ethylmercuri-acetylene is efiectiveas a blue stain preventative. Thus, for example, a mixture conwhitecrystalline material which melts at 959 c. It appears to have theformula The product is readily soluble in cold water, sodium carbonateand caustic soda solutions as well as in acetone, methanol and ethanol.The compound does not deposit mercuric oxide when treated with causticsoda and yields metallic mercury slowly on the addition of sodiumstannite.' It is an excellent germicide and fungicide although not quiteas effective as the compound of Example 1.

By suitable control of the proportions of the same reactants so thatonly one molecule of urea reacts with the alkoxyalkyl-mercuri-acetylene,

a compound having the apparent formula Example 3 10 parts ofbis-gamma-methoxypropyl-mercurl-acetylene and 4 parts of succinimide aredissolved in about 200 parts of dioxan. The solution is refluxed forabout two hours at which time the reaction is complete, and the solventis removed as by vacuum distillation. The reactaining 5% to 10% of thiscompound and 95% to tion product, which appears to have the formula H:CO

90% of sodium carbonate is dissolved in about 400 times its weight inwater to form an impregnating solution which is especially suitable forthis purpose. The wood, either green or partially dried, is dipped intothis impregnating solution and the wood is thereby protected against theaction of stain and rot fungi.

This phthalimide compound is also especially suitable as a dry seeddisinfectant. For this pur- Example 2 10 parts of bis-betaethoxyethyl-mercuriacetylene and 3 parts of urea are dissolved in about200 parts of sec.-butyl alcohol. The solution is refluxed for about 2 /2hours, at which v time the reaction is complete, and the solvent isremoved as by vacuum distillation. The reaction productis dried with theformation of a is dried in vacuo. The product is soluble in water,aqueous sodium carbonate, acetone, methanol and is an effectivegermicide and fungicide. In general, it has substantially the propertiesof the compound of Example. 2.

If desired, the compounds bis-beta-ethoxyethyl-mercuri acetylene, bisdelta propyloxybutyl-mercuri-acetylene,bis-cyclohexyloxyethylmercuri-acetylene and the like may be reacted withsuccinimide as in Example 3 to obtain products similar to that obtainedin accordance with this example.

Example 4 10 parts of bis-methoxy-cyclohexyl-mercuriacetylene and 2.5parts of acetamide are dissolved in about parts of sec.-butyl acetate.The solution is refluxed for about two hours, at which time the reactionis completed, and the solvent is removed by vacuum distillation. Thereaction product is dried in vacuo. It appears to have the formula:

' CHa-CO-NH-CcHro-Hg-Ca The compound produced in accordance with thisexample has substantially the properties of the compounds produced inaccordance with the preceding examples.

Example parts of bis-beta-methoxyethyl-mercuriacetylene and 6 parts ofbenzenesulfonamide are dissolved in about 200 parts of toluene. Thesolution is refluxed for about two hours, at whichtime the reaction iscomplete, and the solvent is removed as by vacuum distillation. Thereaction product is dried with the formation of a white crystallinepowder which appears to have the probable formula:

The compound produced in accordance with this example has substantiallythe properties of the compounds produced in accordance with thepreceding examples.

I claim:

1. A symmetrical organic mercury compound of the general structuralformula (A)R- HgCEC-HgR-(A) wherein (A) is an organicnitrogen-containing radical of the class consisting of the radicalsCO--III and SO21II 3. The compound having the formula CH3CONHCsH1oHgCEC--HgCsHrol\'HCO-CH3 4. The compound having the formula 5. The method ofpreparing soluble organic mercury compounds which comprises reacting amercuri-acetylide compound having the general formula wherein R1represents an alkyl group and R: a hydrocarbon radical ofthe classconsisting of the aliphatic and alicyclic radicals, with an organicnitrogen compound having a radical of the class consisting of theradicals containing a replaceable hydrogen atom.

6. The method of preparing soluble organic mercury compounds whichcomprises reacting a mercuri-acetylide compound having the generalwherein R1 represents an alkyl group and R: a hydrocarbon radical of theclass consisting of the aliphatic and alicyclic radicals, with urea.

7. The method of preparing soluble organic mercury compounds whichcomprises reacting a mercuri-acetylide compound having the generalformula wherein R1 represents an alkyl group and R: a hydrocarbonradical of the class consisting of the aliphatic and alicyclic radicals,with acetamide.

8. The method of preparing soluble organic mercury compounds whichcomprises reacting a mercuri-acetylide compound having the generalformula wherein R1 represents an alkyl group and R2 a hydrocarbonradical of the class consisting of the aliphatic and-alicyclic radicals,with an organic sulfonamide.

9. The method of preparing soluble organic mercury compounds whichcomprises reacting a mercuri-acetylide compound having the generalformula wherein R1 represents an alkyl group and R: a hydrocarbonradical of the class consisting of the aliphatic and alicyclic radicals,with benzene sul fonamide.

MORRIS H. DASKAIS.

CERTIFICATE OF CORRECTION. Patent No. 2,529, 85. September 21, 1915.

MORRIS H. DASKAIS.

It 1e hereby certi fi ed that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 2,first column, line 18, for "acetylate" read --acetylene--; and that thesaid Letters Patent should be read with this correction therein that thesame may confonn to the record of the case in the Fatent Office.

Signed and sealed this 25rd day of November, A. D. 1915.

Henry Van Arsdale, (Seal) Acting Commissioner of Patents.

